Alkylation process

ABSTRACT

The present invention provides an improved process for producing an alkylated aromatic compound from an at least partially untreated alkylatable aromatic compound having catalyst poisons and an alkylating agent, wherein said alkylatable aromatic compound stream is treated to reduce catalyst poisons with a treatment composition having a surface area/surface volume ratio of greater than or equal to 30 in −1  (12 cm −1 ) in a treatment zone separate from an alkylation reaction zone under treatment conditions including a temperature of from about 30° C. to about 300° C. to form an effluent comprising said treated alkylatable aromatic compound.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 13/642,676, filed Jan. 7, 2013, now allowed, which is a NationalStage Application of International Application No. PCT/US2011/032661,filed Apr. 15, 2011, which claims priority to and the benefits of U.S.Provisional patent application Ser. No. 61/346,763, filed May 20, 2010(2010EM130), the contents of which are fully incorporated by referenceherein.

FIELD

The present invention relates to an improved process for producing analkylated aromatic compound from an at least partially untreatedalkylatable aromatic compound stream and an alkylating agent, whereinsaid at least partially alkylatable aromatic compound stream containscatalyst poisons which are at least partially removed by contacting witha treatment composition. In particular, this invention relates toprocesses to produce ethylbenzene, cumene and sec-butylbenzene frombenzene streams which contain catalyst poisons which are at leastpartially removed by contacting with treatment composition which arepreferably porous crystalline materials.

BACKGROUND

Of the alkylaromatic compounds advantageously produced by the presentimproved process, ethylbenzene and cumene, for example, are valuablecommodity chemicals which are used industrially for the production ofstyrene monomer and coproduction of phenol and acetone respectively. Infact, a common route for the production of phenol comprises a processwhich involves alkylation of benzene with propylene to produce cumene,followed by oxidation of the cumene to the corresponding hydroperoxide,and then cleavage of the hydroperoxide to produce equimolar amounts ofphenol and acetone. Ethylbenzene may be produced by a number ofdifferent chemical processes. One process which has achieved asignificant degree of commercial success is vapor phase alkylation ofbenzene with ethylene in the presence of a solid, acidic ZSM-5 zeolitecatalyst. Examples of such ethylbenzene production processes aredescribed in U.S. Pat. No. 3,751,504 (Keown), U.S. Pat. No. 4,547,605(Kresge) and U.S. Pat. No. 4,016,218 (Haag). U.S. Pat. No. 5,003,119(Sardina) describes the use of zeolites X, Y, L, Beta, ZSM-5, Omega, andmordenite and chabazite in synthesis of ethylbenzene. U.S. Pat. No.5,959,168 (van der Aalst) describes the use of zeolites Y, Beta, MCM-22,MCM-36, MCM-49 and MCM-56 in synthesis of ethylbenzene in a plantdesigned for use of aluminum chloride-based catalyst.

Another process which has achieved significant commercial success isliquid phase alkylation for producing ethylbenzene from benzene andethylene since it operates at a lower temperature than the vapor phasecounterpart and hence tends to result in lower yields of by-products.For example, U.S. Pat. No. 4,891,458 (Innes) describes the liquid phasesynthesis of ethylbenzene with zeolite beta, whereas U.S. Pat. No.5,334,795 (Chu) describes the use of MCM-22 in the liquid phasesynthesis of ethylbenzene; and U.S. Pat. No. 7,649,122 (Clark) describesthe use of MCM-22 in the liquid phase synthesis of ethylbenzene in thepresence of a maintained water content. U.S. Pat. No. 4,549,426 (Inwood)describes the liquid phase synthesis of alkylbenzene with steamstabilized zeolite Y. U.S. Patent Publication No. 2009/0234169 A1(Pelati) describes the liquid phase aromatic alkylation over at leastone catalyst bed containing a first catalyst modified by inclusion of arare earth metal ion.

Cumene has been produced commercially by the liquid phase alkylation ofbenzene with propylene over a Friedel-Craft catalyst, particularly solidphosphoric acid or aluminum chloride. Zeolite-based catalyst systemshave been found to be more active and selective for propylation ofbenzene to cumene. For example, U.S. Pat. No. 4,992,606 (Kushnerick)describes the use of MCM-22 in the liquid phase alkylation of benzenewith propylene.

Other publications show use of catalysts comprising crystalline zeolitesfor conversion of feedstock comprising an alkylatable aromatic compoundand an alkylating agent to alkylaromatic conversion product under atleast partial liquid phase conversion conditions. These include U.S.2005/0197517A1 (Cheng); U.S. 2002/0137977A1 (Hendrickson); and U.S.2004/0138051A1 (Shan) showing use of a catalyst comprising a microporouszeolite embedded in a mesoporous support; WO 2006/002805 (Spam); andU.S. Pat. No. 6,376,730 (Jan) showing use of layered catalyst; EP0847802B1; and U.S. Pat. No. 5,600,050 (Huang) showing use of catalystcomprising 30 to 70 wt. % H-Beta zeolite, 0.5 to 10 wt. % halogen, andthe remainder alumina binder.

Other such publications include U.S. Pat. No. 5,600,048 (Cheng)describing preparing ethylbenzene by liquid phase alkylation over acidicsolid oxide such as MCM-22, MCM-49 and MCM-56, Beta, X, Y or mordenite;U.S. Pat. No. 7,411,101 (Chen) describing preparing ethylbenzene orcumene by liquid phase alkylation over acidic solid oxide such as PSH-3,ITQ-2, MCM-22, MCM-36, MCM-49, MCM-56, and Beta at conversion conditionsincluding a temperature as high as 482° C. and pressure as high as13,788 kPa; and U.S. Pat. No. 7,645,913 (Clark) describing preparingalkylaromatic compounds by liquid phase alkylation in a multistagereaction system over acidic solid oxide catalyst in the first reactionzone having more acid sites per unit volume of catalyst than thecatalyst in the second reaction zone at conversion conditions includingfor ethylbenzene a temperature as high as 270° C. and pressure as highas 8,300 kPa, and for cumene a temperature as high as 250° C. andpressure as high as 5,000 kPa. U.S. Patent Publication No. 2008/0287720A1 (Clark) describes alkylation of benzene over catalyst of MCM-22family material in a reaction zone having water content maintained atfrom 1 to 900 wppm. U.S. Patent Publication No. 2009/0137855 A1 (Clark)describes a mixed phase process for producing alkylaromatic compoundsfrom a dilute alkene feedstock which also includes alkane impurities. Inthe latter publication, the volume ratio of liquid to vapor in thefeedstock is from 0.1 to 10.

A problem common to processes using zeolites, for example, alkylationprocesses for producing alkylaromatic compounds, such as ethylbenzeneand cumene, is reduced operational life of the catalyst because ofdeactivation caused by various catalyst poisons present in the feedstockto the processes. First step guard beds or separation zones containingpoison adsorbents such as clay, resins, molecular sieves and the likemay be employed to limit such poisons in the feedstock. Such feedstockincludes, but is not limited to, an alkylatable aromatic feedstock, suchas a benzene feedstock. Examples of publications showing this includeU.S. Pat. No. 6,894,201 B1 (Schmidt) using clay, molecular sieve orresin adsorbents; U.S. Pat. No. 5,744,686 (Gajda) using a non-acidicmolecular sieve having a silica/alumina ratio in excess of 100 and anaverage pore size less than 5.5 Angstroms such as zeolite 4 A and ZSM-5;and U.S. Patent Publication No. 2005/0143612 A1 (Hwang) usingdistillation, extraction or adsorption over acidic clay, zeolite,activated alumina, activated carbon, silica gel, and ion exchange resin.Feedstock pretreatment is also shown in U.S. Pat. No. 7,199,275 B2(Smith) involving contact with a first molecular sieve having a Si/Almolar ratio less than 5, e.g., 13 X, followed by contact with a secondmolecular sieve having a Si/A1 molar ratio of greater than 5, e.g., 4 A;and in U.S. Patent Publication No. 2009/0259084 A1 (Smith) involvingcontact with a first molecular sieve comprising zeolite X, followed bycontact with a second molecular sieve comprising zeolite Y.

In WO98/07673 (Samson), a process of preparing an alkylated benzene ormixture of alkylated benzenes involving contacting a benzene feedstockwith a solid acid, such as an acidic clay or acid zeolite, in apretreatment zone at a temperature greater than about 130° C. but lessthan about 300° C. to form a pretreated benzene feedstock, andthereafter contacting the pretreated benzene feedstock with (a) analkylating agent in an alkylation zone or (b) a transalkylating agent ina transalkylation zone, in the presence of an alkylation/transalkylationcatalyst so as to prepare the alkylated benzene or mixture of alkylatedbenzenes. The pretreatment step is said to improve the lifetime of thealkylation/transalkylation catalyst. Preferred products are ethylbenzeneand cumene.

A single alkylation reaction zone containing catalyst having surfacearea to volume ratios within prescribed ranges is shown in U.S. Pat. No.6,888,037 B2 (Dandekar) where cumene is manufactured in the liquid phaseover catalyst having surface area/volume of 80 to 200 in⁻¹ (31 to 79cm⁻¹), preferably from 100 to 150 in (39 to 59 cm⁻¹). A single reactionzone is shown in an alkylation process in U.S. Pat. No. 7,816,574 B2(Clark) wherein the catalyst therein is a particulate material of from125 to 790 microns in size with a surface area/volume of greater than 79in⁻¹ (31 cm⁻¹). U.S. Pat. No. 5,118,896 (Steigelmann) shows an aromaticalkylation process using a single alkylation reaction zone, i.e., acatalytic distillation reactor, with catalyst having a pore volume of0.25 to 0.50 cc/g and pores having a radius greater than 450 Angstromsand a catalyst particle diameter of not more than 1/32 inch (0.08 cm).U.S. Pat. No. 4,185,040 (Ward) shows an aromatic alkylation processusing a single alkylation reaction zone with zeolite Y catalyst having aratio of external surface area/volume of 85 to 160 in⁻¹ (34 to 63 cm⁻¹).

U.S. Patent Publication No. 2009/0306446 A1 (Clark) shows a process forproducing monoalkylated aromatics in a single reaction zone having twodifferent catalysts, the first catalyst having a surface area/volumeratio greater than 79 cm⁻¹, and a second catalyst comprising particleshaving a surface area/volume between 78 and 79 cm⁻¹.

Existing alkylation processes for producing alkylaromatic compounds, forexample, ethylbenzene and cumene, inherently produce polyalkylatedspecies as well as the desired monoalkyated product. It is thereforenormal to transalkylate the polyalkylated species with additionalaromatic feed, for example benzene, to produce additional monoalkylatedproduct, for example ethylbenzene or cumene, either by recycling thepolyalkylated species to the alkylation reactor or, more frequently, byfeeding the polyalkylated species to a separate transalkylation reactor.Examples of catalysts which have been used in the alkylation of aromaticspecies, such as alkylation of benzene with ethylene or propylene, andin the transalkylation of polyalkylated species, such aspolyethylbenzenes and polyisopropylbenzenes, are listed in U.S. Pat. No.5,557,024 (Cheng) and include MCM-49, MCM-22, PSH-3, SSZ-25, zeolite X,zeolite Y, zeolite Beta, acid dealuminized mordenite and TEA-mordenite.Transalkylation over a small crystal (<0.5 micron) form of TEA-mordeniteis also disclosed in U.S. Pat. No. 6,984,764.

Where the alkylation step is performed in the liquid phase, it is alsodesirable to conduct the transalkylation step under liquid phaseconditions. However, by operating at relatively low temperatures, liquidphase processes impose increased requirements on the catalyst,particularly in the transalkylation step where the bulky polyalkylatedspecies must be converted to additional monoalkylated product withoutproducing unwanted by-products. This has proven to be a significantproblem in the case of cumene production where existing catalysts haveeither lacked the desired activity or have resulted in the production ofsignificant quantities of by-products such as ethylbenzene andn-propylbenzene.

Although it is suggested in the art that catalysts for conversion offeedstock comprising an alkylatable aromatic compound and an alkylatingagent to alkylaromatic conversion product under at least partial liquidphase conversion conditions are composed of a porous crystallinematerial, e.g., aluminosilicate molecular sieves, having an MWWframework structure type, the present improved process has not beentaught. Finding a commercially acceptable method for such processesconducted under at least partial liquid phase conversion conditionswhich delays alkylation catalyst deactivation and does not negativelyaffect monoselectivity, i.e., lower di- or polyalkyl product make, wouldallow capacity expansion in existing plants and lower capital expensefor grassroots plants.

According to the present invention, an improved process was unexpectedlydiscovered for producing an alkylated aromatic compound from an at leastpartially untreated alkylatable aromatic compound stream and analkylating agent, wherein said alkylatable aromatic compound streamcontains catalyst poisons which are at least partially removed bycontacting with a treatment composition. This is especially the casewhen the process is to produce ethylbenzene, cumene and sec-butylbenzenefrom benzene streams which contain catalyst poisons which are at leastpartially removed by contacting with treatment composition which arepreferably porous crystalline materials.

SUMMARY

According to the present invention, there is provided an improvedprocess for producing an alkylated aromatic compound stream from an atleast partially untreated alkylatable aromatic compound stream havingcatalyst poisons and an alkylating agent stream. Preferably, thealkylated aromatic compound is a monoalkylated aromatic compound such asethylbenzene, cumene and sec-butylbenzene; preferably, the alkylatablearomatic compound is benzene; and preferably, the alkylating agent isethylene, propylene or butene. The untreated alkylatable aromaticcompound stream is treated with a treatment composition having a highsurface area/volume ratio and in the presence of the alkylating agent inorder to reduce catalyst poisons.

One embodiment of the process of this invention comprises the steps of:(a) contacting an at least partially untreated alkylatable aromaticcompound stream having said catalyst poisons and an alkylating agentstream with a treatment composition in a treatment zone separate from,and preferably upstream from, an alkylation reaction zone undertreatment conditions to remove at least a portion of said catalystpoisons and to alkyate at least a portion of said alkylatable aromaticcompound to form a treated effluent stream which comprises treatedalkylatable aromatic compound, an alkylated aromatic compound and areduced amount of catalyst poisons, wherein said treatment compositionhas a surface area/surface volume ratio of greater than 30 in⁻¹ (12cm⁻¹), said treatment conditions include a temperature of from about 30°C. (ambient) to about 300° C. and a pressure from about 101 kPa(ambient) to about 4601 kPa, and a molar ratio of untreated alkylatablearomatic compound to alkylating agent of greater than or equal to about25:1; and (b) contacting said treated alkylatable aromatic compound insaid effluent stream and additional said alkylating agent stream with acatalyst composition in said alkylation reaction zone separate from, andpreferably downstream from, said treatment zone under at least partialliquid phase catalytic conversion conditions to form an alkylatedeffluent stream which comprises additional alkylated aromatic compound,wherein said catalyst composition comprises a porous crystallinematerial having a framework structure type selected from the groupconsisting of FAU, *BEA, MOR, MWW and mixtures thereof, wherein said atleast partial liquid phase catalytic conversion conditions include atemperature of from about 100° C. to about 300° C., a pressure fromabout 689 kPa to about 4601 kPa, a molar ratio of treated alkylatablearomatic compound to alkylating agent of from about 0.01:1 to about25:1, and a feed weight hourly space velocity (WHSV) based on alkylatingagent of from about 0.5 to about 500 hr⁻¹.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, the term “alkylatable aromatic compound” means acompound that may receive an alkyl group and an “alkylating agent” is acompound which may donate an alkyl group.

The term “aromatic” in reference to the alkylatable aromatic compoundswhich may be useful as feedstock herein is to be understood inaccordance with its art-recognized scope. This includes alkylsubstituted and unsubstituted mono- and polynuclear compounds. Compoundsof an aromatic character that possess a heteroatom are also usefulprovided they do not act as catalyst poisons under the reactionconditions selected.

The term “catalyst poisons” means an impurity present in the at leastpartially untreated alkylatable aromatic compound stream, particularlythe benzene stream, which comprise one or more compounds which containat least one of the following elements: nitrogen, halogens, oxygen,sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 throughGroup 12 metals.

As used herein, the term “liquid or partial liquid phase” in referenceto the present improved process means that the reaction mixturecomprises greater than or equal to 10 volume percent liquid, for examplegreater than or equal to 30 volume percent liquid, up to 100 volumepercent liquid.

As used herein, the term “surface area/surface volume ratio” means theratio obtained by dividing the surface area of the formulated particleby the geometric surface volume of the formulated particle. As usedherein, the term “geometric surface volume” means the volume of theformulated particle calculated as though the particle is a solidparticle without regard to the volume of any pores, channels or chamberson the surface or inside of the formulated particle. For example, for ageometric sphere, the surface area/surface volume ratio (SN) is 3/r,where r is the radius of the particle.

As used herein, the term “untreated alkylatable aromatic compound” meansa stream which contains an alkylatable aromatic compound and anycatalyst poisons before it is contacted with the treatment compositionof this invention. For the avoidance of doubt, such untreatedalkylatable aromatic compound may have been subjected to other treatmentsteps in upstream or downstream processes in which at least a portion ofcatalyst poisons may have been removed, such that there are remainingcatalyst poisons for removal by the process of this invention.

As used herein, the term “wppm” means parts-per-million by weight.

Treatment Composition

In one or more embodiments, the treatment composition for use in thepresent improved process comprises preferably a porous crystallinematerial and has a surface area/surface volume ratio of greater than orequal to 30 in⁻¹ (12 cm⁻¹); or a surface area/surface volume ratio ofgreater than or equal to 50 in⁻¹ (20 cm⁻¹); or a surface area/surfacevolume ratio of greater than or equal to 75 in⁻¹ (30 cm⁻¹); or a surfacearea/surface volume ratio of greater than or equal to 125 in⁻¹ (50cm⁻¹); or a surface area/surface volume ratio of greater than or equalto 250 in⁻¹ (99 cm⁻¹); or a surface area/surface volume ratio of greaterthan or equal to 500 in⁻¹ (197 cm⁻¹).

The surface area/surface volume ratio of the treatment composition is inthe range of greater than or equal to 30 in⁻¹ (12 cm⁻¹) to less than orequal to 70 in⁻¹ (28 cm⁻¹); or in the range of greater than or equal to75 in⁻¹ (30 cm⁻¹) to less than or equal to 125 in⁻¹ (49 cm⁻¹); or in therange of greater than or equal to 125 in⁻¹ (49 cm⁻¹) to less than orequal to 250 in⁻¹ (98 cm⁻¹); or in the range of greater than or equal to250 in⁻¹ (98 cm⁻¹) to less than or equal to 500 in⁻¹ (197 cm⁻¹); or inthe range of 70 in⁻¹ (28 cm⁻¹) to 100 in⁻¹ (39 cm⁻¹); or in the range of180 in⁻¹ (71 cm⁻¹) to 220 in⁻¹ (87 cm⁻¹); or in the range of 600 in⁻¹(236 cm⁻¹) to 770 in⁻¹ (303 cm⁻¹).

The method of making the treatment composition having the desiredsurface area/surface volume ratio is not particularly limited. One ormore of the long-known techniques, such as spray drying, prilling,pelletizing and extrusion, have been and are being used to producemacrostructures in the form of, for example, spherical particles,extrudates, pellets and tablets. A summary of these techniques isdescribed in Catalyst Manufacture by A. B. Stiles and T. A. Koch, MarcelDekker, New York, 1995.

The treatment composition having the desired surface area/surface volumeratio may be made, for example, by controlling its particle size (i.e.,crushed particles).

The treatment composition having the desired surface area/surface volumeratio may also be made, for example, by using a shaped treatmentcomposition. Non-limiting examples of shaped treatment compositions,include hollow or solid polylobal extrudates made by extrusion asdescribed in U.S. Pat. No. 4,441,990 (Huang); hollow shaped extrudatesas described in U.S. Pat. No. 7,198,845 (Van Hasselt); longitudinallychanneled cylindrical extrudates as described in U.S. Pat. No. 4,432,643(Kyan); grooved cylindrical extrudates as described in U.S. Pat. No.4,328,130.

For example, a cylindrically-shaped treatment composition having adiameter of 1/32 inch (0.08 cm) and a length of 3/32 inch (0.24 cm) hasa surface area/surface volume ratio of 141 in⁻¹ (56 cm⁻¹). A treatmentcomposition as a quadralobal solid extrudate having the external shapedisclosed in FIG. 4 of U.S. Pat. No. 4,441,990 and having a maximumcross-sectional dimension of 1/16 inch (0.16 cm) and a length of 3/16inch (0.48 cm) has a surface area/surface volume ratio of 128 in⁻¹ (50cm⁻¹). A treatment composition as a hollow tubular extrudate having anexternal diameter of 1/10 inch (0.25 cm), an internal diameter of 1/30inch (0.08 cm) and a length of 3/10 inch (0.75 cm) has a surfacearea/surface volume ratio of 136 in⁻¹ (54 cm⁻¹).

The surface area/volume ratio may be determined by measuring a physicaldimension and the curvature of the treatment composition particle, andthen calculating the surface area and volume based on known equations ofgeometry.

The treatment compositions of this invention may comprise one or amixture of molecular sieves, and must have any particle shapes orconfiguration to allow for the required surface area/surface volumeratio.

The treatment composition as porous crystalline molecular sieves mayhave, as non-limiting examples, the structure of *BEA, including zeoliteBeta (described in U.S. Pat. No. 3,308,069); the structure of FAU,including faujasite, zeolite Y, Ultrastable Y (USY, described in U.S.Pat. Nos. 3,293,192 and 3,449,070), Dealuminized Y (Deal Y, preparationof which is described in U.S. Pat. No. 3,442,795), rare earth exchangedY (REY, described in U.S. Pat. No. 4,415,438), Ultrahydrophobic Y(UHP-Y, described in U.S. Pat. No. 4,401,556); the structure of MOR,including mordenite (a naturally occurring material), and TEA-mordenite(a synthetic mordenite prepared from a reaction mixture comprising atetraethylammonium directing agent, disclosed in U.S. Pat. Nos.3,766,093 and 3,894,104). The treatment composition may include mixturesof the above porous crystalline molecular sieves. Other suitable porouscrystalline molecular sieves include, but are not limited to, ZSM-3,ZSM-4, ZSM-5, ZSM-14, ZSM-18, and ZSM-20, including mixtures thereof.

In one or more embodiments, the treatment composition may also beselected from the group consisting of clay, resin, solid phosphoricacid, activated alumina, Linde type X, such as 13 X, a Linde type A,such as 4 A or 5 A. and mixtures thereof, as non-limiting examples.

A summary of the molecular sieves and/or zeolites, in terms ofproduction, modification and characterization of molecular sieves, isdescribed in Molecular Sieves-Principles of Synthesis and Identificationby R. Szostak, Blackie Academic & Professional, London, 1998, SecondEdition. In addition to molecular sieves, amorphous materials, chieflysilica, aluminum silicate and aluminum oxide, have been used asadsorbents and catalyst supports.

Catalytic Composition

The catalytic composition suitable for use in the present inventioncomprises a porous crystalline material having a framework structuretype selected from the group consisting of FAU, *BEA, MOR, MWW andmixtures thereof, preferably MWW framework structure.

Porous crystalline materials having a FAU framework structure typeinclude faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (DealY), Rare Earth Y (REY), Ultrahydrophobic Y (UHP-Y), described above, ormixtures thereof.

A porous crystalline material having a *BEA framework structure type iszeolite beta, described above.

A porous crystalline materials having a MOR framework structure type ismordenite, TEA-mordenite, described above, or a mixture thereof.

Porous crystalline materials having MWW framework structure typegenerally have an X-ray diffraction pattern including d-spacing maximaat 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms. The X-raydiffraction data used to characterize the material are obtained bystandard techniques using the K-alpha doublet of copper as the incidentradiation and a diffractometer equipped with a scintillation counter andassociated computer as the collection system.

Examples of MWW framework structure type materials include MCM-22(described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S. Pat.No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1(described in European Patent No. 0293032), ITQ-1 (described in U.S.Pat. No. 6,077,498), ITQ-2 (described in U.S. Pat. No. 6,231,751),ITQ-30 (described in WO 2005-118476), MCM-36 (described in U.S. Pat. No.5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575), MCM-56(described in U.S. Pat. No. 5,362,697) and UZM-8 (described in U.S. Pat.No. 6,756,030).

Preferably, the catalytic composition comprising a porous crystallinematerial having MWW framework structure type is PSH-3, SSZ-25, ERB-1,ITQ-1, ITQ-2, ITQ-30, MCM-22, MCM-36, MCM-49, MCM-56, UZM-8, EMM-10,EMM-12, EMM-13 or mixtures thereof.

In an embodiment of the invention, the catalyst will have a RelativeActivity measured as an RA₂₂₀ of at least 8.6, for example from 8.6 to12.0, or RA₁₈₀ of at least 3.5, for example from 3.5 to 6.0.

Methods for producing the catalysts required for use in the presentinvention comprise those taught in the publications listed herein andincorporated herein by reference. For example, U.S. Pat. No. 4,954,325describes crystalline MCM-22 and catalyst comprising same, U.S. Pat. No.5,236,575 describes crystalline MCM-49 and catalyst comprising same, andU.S. Pat. No. 5,362,697 describes crystalline MCM-56 and catalystcomprising same.

Binders

The catalyst composition and treatment composition for use in thepresent invention may include an inorganic oxide matrix material orbinder. Such matrix or binder materials include synthetic or naturallyoccurring substances as well as inorganic materials such as clay, silicaand/or metal oxides. The latter may be either naturally occurring or inthe form of gelatinous precipitates or gels including mixtures of silicaand metal oxides. Naturally occurring clays which can be composited withthe inorganic oxide material include those of the montmorillonite andkaolin families, which families include the subbentonites and thekaolins commonly known as Dixie, McNamee, Georgia and Florida clays orothers in which the main mineral constituent is halloysite, kaolinite,dickite, nacrite or anauxite. Such clays can be used in the raw state asoriginally mined or initially subjected to calcination, acid treatmentor chemical modification.

Specific useful matrix or binder materials employed herein includesilica, alumina, zirconia, titania, silica-alumina, silica-magnesia,silica-zirconia, silica-thoria, silica-beryllia, silica-titania as wellas ternary compositions such as silica-alumina-thoria,silica-alumina-zirconia, silica-alumina-magnesia andsilica-magnesia-zirconia. The matrix can be in the form of a cogel. Amixture of these components could also be used.

For the improvement of the present invention, relative proportions ofthe crystalline molecular sieve and binder or matrix are not especiallycritical.

The catalyst for use in the present invention, or its crystallinemolecular sieve component, may or may not contain addedfunctionalization, such as, for example, a metal of Group VI (e.g., Crand Mo), Group VII (e.g., Mn and Re) or Group VIII (e.g., Co, Ni, Pd andPt), or phosphorus.

Alkylatable Aromatics, Alkylating Agents and Products

Alkylatable aromatic compounds suitable for the present inventioninclude substituted aromatic compounds that can be alkylated mustpossess at least one hydrogen atom directly bonded to the aromaticnucleus. The aromatic rings can be substituted with one or more alkyl,aryl, alkaryl, alkoxy, aryloxy, cycloalkyl, halide, and/or other groupsthat do not interfere with the alkylation reaction.

Suitable alkylatable aromatic compounds include benzene, naphthalene,anthracene, naphthacene, perylene, coronene, and phenanthrene, withbenzene being preferred.

Generally the alkyl groups that can be present as substituents on thearomatic compound contain from 1 to about 22 carbon atoms and usuallyfrom about 1 to 8 carbon atoms, and most usually from about 1 to 4carbon atoms.

Suitable alkylatable aromatics compounds include alkyl substitutedaromatic compounds include toluene, xylene, isopropylbenzene,n-propylbenzene, alpha-methylnaphthalene, ethylbenzene, mesitylene,durene, cymenes, butylbenzene, pseudocumene, o-diethylbenzene,m-diethylbenzene, p-diethylbenzene, isoamylbenzene, isohexylbenzene,pentaethylbenzene, pentamethylbenzene; 1,2,3,4-tetraethylbenzene;1,2,3,5-tetramethylbenzene; 1,2,4-triethylbenzene;1,2,3-trimethylbenzene, m-butyltoluene; p-butyltoluene;3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene; m-propyltoluene;4-ethyl-m-xylene; dimethylnaphthalenes; ethylnaphthalene;2,3-dimethylanthracene; 9-ethylanthracene; 2-methylanthracene;o-methylanthracene; 9,10-dimethylphenanthrene; and3-methyl-phenanthrene. Higher molecular weight alkylaromatic compoundscan also be used as starting materials and include aromatic organicssuch as are produced by the alkylation of aromatic organics with olefinoligomers. Such products are frequently referred to in the art asalkylate and include hexylbenzene, nonylbenzene, dodecylbenzene,pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene,pentadecytoluene, etc. Very often alkylate is obtained as a high boilingfraction in which the alkyl group attached to the aromatic nucleusvaries in size from about C₆ to about C₁₂. When cumene or ethylbenzeneis the desired product, the present process produces acceptably littleby-products such as xylenes. The xylenes made in such instances may beless than about 500 ppm.

Reformate containing a mixture of benzene, toluene and/or xyleneconstitutes a useful feed for the processes of this invention.

Suitable alkylating agents for the present invention include olefinssuch as ethylene and propylene; alcohols (inclusive of monoalcohols,dialcohols, trialcohols, etc.) such as methanol, ethanol and thepropanols; aldehydes such as formaldehyde, acetaldehyde andpropionaldehyde; and alkyl halides such as methyl chloride, ethylchloride and the propyl chlorides, and so forth.

Mixtures of light olefins are useful as alkylating agents in thealkylation process of this invention. Accordingly, mixtures of ethyleneand propylene which are major constituents of a variety of refinerystreams, e.g., fuel gas, gas plant off-gas containing ethylene,propylene, etc., naphtha cracker off-gas containing light olefins,refinery FCC propane/propylene streams, etc., are useful alkylatingagents herein. For example, a typical FCC light olefin stream possessesthe following composition:

Wt. % Mole % Ethane 3.3 5.1 Ethylene 0.7 1.2 Propane 4.5 15.3 Propylene42.5 46.8 Isobutane 12.9 10.3 n-Butane 3.3 2.6 Butenes 22.1 18.32Pentanes 0.7 0.4

Non-limiting examples of reaction products that may be obtained from theprocess of the present invention include ethylbenzene from the reactionof benzene with ethylene, cumene from the reaction of benzene withpropylene, ethyltoluene from the reaction of toluene with ethylene andcymenes from the reaction of toluene with propylene. Particularlypreferred process mechanisms of the invention relate to the productionof cumene by the alkylation of benzene with propylene, and production ofethylbenzene by the alkylation of benzene with ethylene.

The reactants for the present improved process can be in partially orcompletely liquid phase and can be neat, i.e., free from intentionaladmixture or dilution with other material, or they can be brought intocontact with the required catalyst composition with the aid of carriergases or diluents such as, for example, hydrogen or nitrogen.

Catalyst Poisons and Treatment Process

The at least partially untreated alkylatable aromatic compound streammay contain impurities which can act over time to poison the catalyticcomposition. These catalyst poisons may comprise up to about 10 wppm, orup to 5 wppm, or up to 1 wppm, or up to 0.5 wppm, or up to about 0.1wppm of said at least partially untreated alkylatable aromatic compoundstream. Such catalyst poison may be in the range from at least 1 wppm to5 wppm, or 1 wppm to 10 wppm, or even 5 wppm to 10 wppm by weight ofsaid at least partially untreated alkylatable aromatic compound stream.Such catalyst poisons comprise one or more compounds which contain atleast one of the following elements: nitrogen, halogens, oxygen, sulfur,arsenic, selenium, tellurium, phosphorus, and Group 1 through Group 12metals.

In the present invention, the at least partially untreated alkylatablearomatic compound stream having catalyst poisons is treated bycontacting this stream and an alkylating agent stream with a treatmentcomposition in a treatment zone separate from and upstream from analkylation reaction zone. The contacting is performed under treatmentconditions to remove at least a portion of said catalyst poisons and toalkylate at least a portion of said alkylatable aromatic compound,thereby forming a treated effluent stream which comprises a treatedalkylatable aromatic compound as well as small amount of an alkylatedaromatic compound and a reduced amount of catalyst poisons. As notedabove, the treatment composition comprises a porous crystalline zeolitehaving a high surface area/surface volume ratio.

In one or more embodiments, the treatment conditions include atemperature of from about 30° C. (ambient) to about 300° C., from about100° C. to 200° C., or from about 100° C. to 125° C. The treatmentpressure is from about 101 kPa (ambient) to about 4601 kPa, from about101 kPa to about 3000 kPa, and from about 101 kPa to about 2500 kPa. Thetreatment weight hourly space velocity (WHSV) is in the range from about5 to 70 hr⁻¹, preferably 12 to 45 hr⁻¹, based on the weight of the atleast partially untreated alkylatable aromatic compound.

The treatment composition has the capacity to absorb greater than about100, or greater than about 300, or greater than about 500, or greaterthan about 700, or greater than about 900 micromoles of collidine pergram of treatment composition. The capacity to absorb collidine is inthe range from about 50 up to about 150, from about 150 to about 300,from about 300 to about 500, from about 500 to about 700, from about 700to about 900, from about 900 to about 1000 micromoles of collidine pergram of treatment composition.

The treatment composition has the capacity to absorb greater than about900, or greater than about 1500, or greater than about 2500, or greaterthan about 3500, or greater than about 5500 wppm N-formyl morpholine(NFM) based on the weight of the treatment composition. The capacity toabsorb NFM is in the range from about 900 up to about 1500, from about1500 to about 2500, from about 2500 to about 3500, from about 3500 toabout 5500, from about 5500 to about 7000 wppm NFM based on the weightof the treatment composition.

In operation, the at least partially untreated alkylatable aromaticstream having said catalyst poisons is fed to the treatment zone alongwith the alkylating agent stream. This untreated alkylatable aromaticcompound mixture is contacted with the treatment composition in atreatment zone separate from an alkylation reaction zone under treatmentconditions to remove at least a portion of said catalyst poisons and toalkylate at least a portion of said alkylatable aromatic compound toform a treated effluent stream which comprises treated alkylatablearomatic compound, an alkylated aromatic compound and a reduced amountof catalyst poisons, wherein said treatment composition has a surfacearea/surface volume ratio of greater than 30 in⁻¹ (12 cm⁻¹), saidtreatment conditions include a temperature of from about 30° C. to about300° C. and a pressure from about 101 kPa to about 4601 kPa, and a molarratio of untreated alkylatable aromatic compound to alkylating agent ofgreater than or equal to about 25:1. In the treatment zone, at least onecatalyst poison is absorbed by and strongly bound to the treatmentcomposition causing it to be at least partially removed from the atleast partially untreated alkylatable aromatic compound stream.

The high surface area/volume ratio of the treatment composition and thehigh ratio of the at least partially untreated alkylatable aromaticcompound to alkylating agent (particularly as compared to the catalyticconversion conditions employed in alkylation reactions) providesubstantially improved removal of catalyst poisons from the untreatedalkylatable aromatic compound stream in the treatment zone. Moreover,such catalyst poison removal is further combined at the same time withalkylating at least a portion of said alkylatable aromatic compound toproduce the desired alkylated aromatic compound.

In the treatment zone, the molar ratio of the at least partiallyuntreated alkylatable aromatic compound to alkylating agent of greaterthan or equal to about 10:1; or greater than or equal to about 25:1; orgreater than or equal to about 50:1; or greater than or equal to about75:1; or greater than or equal to about 100:1. The molar ratio of the atleast partially untreated alkylatable aromatic compound to alkylatingagent is in the range of 10:1 to 25:1, or 25:1 to 50:1, or 50:1 to 75:1;or 75:1 to 100:1. In some embodiments, the ratio of at least partiallyuntreated alkylatable aromatic to alkylating agent is in the range of5:1 to 50:1 for a single bed of treatment composition in the treatmentzone.

As a result of the treatment step of the present invention by contactingthe at least partially untreated alkylatable aromatic compound streamwith the treatment composition under the aforementioned treatmentconditions, at least 1 wt. %, at least 5 wt. %, at least 10 wt. %, atleast 15 wt. %, at least 25 wt. %, at least 50 wt. %, at least 75 wt. %,or up to at least 99 wt. % of said catalyst poisons in the at leastpartially untreated alkylatable aromatic compound stream are removed.

In addition, as supplied, most commercial at least partially untreatedalkylatable aromatic compound streams are water saturated, and maycontain up to about 50 wppm, generally up to about 200 wppm, water. Thepresent process provides an advantageous method of reducing the amountsof theses catalyst poisons in commercial at least partially untreatedalkylatable aromatic compound streams to acceptable levels havingaformentioned amounts of water.

Alkylation Process

In the process of this invention, the physical apparatus used for thetreatment zone and that for the alkylation reaction zone may be, forexample, separated and in series whereby the effluent from the treatmentzone is then recovered and fed to the downstream reaction zone. Also,the same apparatus may be used for both the treatment zone and thealkylation reaction zone so long as all alkylatable aromatic compoundcontacts the treatment composition in the treatment zone at thetreatment conditions before effluent comprising the treated alkylatablearomatic compound contacts the alkylation catalyst at alkylationconversion conditions in the separate portion of the reaction zone. Inthe latter situation, of course, the effluent from the treatment zone ofstep (a) above comprising treated alkylatable aromatic compound and anyunreacted alkylating agent would pass directly to the alkylationreaction zone of step (b) above.

The improved alkylation process of this invention may be conducted suchthat the reactants, i.e., the effluent from the treatment zonecomprising treated alkylatable aromatic compound are brought intocontact with the catalytic composition in a suitable reaction zone suchas, for example, in a flow reactor containing a fixed bed of thecatalyst composition, under effective catalytic conversion conditions.Preferably, at least partial liquid phase catalytic conversionconditions which include a temperature of from about 100° C. to about300° C., preferably from about 100° C. to about 285° C., most preferablyfrom about 100° C. to about 200° C., a pressure of from about 689 toabout 4601 kPa, preferably from about 689 to about 3102 kPa, a molarratio of treated alkylatable aromatic compound to alkylating agent offrom about 0.1:1 to about 25:1, preferably from about 0.5:1 to about10:1, and a feed weight hourly space velocity (WHSV) based on thealkylating agent of from about 0.1 to 500 hr⁻¹, preferably from about0.5 to about 100 hr⁻¹.

When the treated alkylatable aromatic compound comprises treated benzeneand the alkylating agent is ethylene to produce ethylbenzene, thealkylation reaction is preferably carried out under at least partialliquid phase catalytic conversion conditions including a temperature offrom about 100° C. to about 280° C., from about 100° C. to about 230°C., preferably from about 125° C. to about 260° C.; a pressure up toabout 4601 kPa, preferably from about 689 kPa to about 3102 kPa; aweight hourly space velocity (WHSV) based on the ethylene alkylatingagent of from about 0.1 to about 20 hr⁻¹, preferably from about 0.5 toabout 6 hr⁻¹; and a ratio of treated benzene to ethylene in thealkylation reaction zone of from about 0.1:1 to about 30:1 molar,preferably from about 1:1 to about 20:1 molar.

When the treated alkylatable aromatic compound comprises treated benzeneand the alkylating agent is propylene to produce cumene, the reactionmay also take place under at least partial liquid phase catalyticconversion conditions including a temperature of less than about 200°C., from about 100 to about 200° C., from about 125° C. to about 180°C.; a pressure of about 3102 kPa or less, e.g., from about 1724 kPa toabout 3102 kPa; a weight hourly space velocity (WHSV) based on propylenealkylating agent of from about 0.1 hr⁻¹ to about 25 hr⁻¹, preferablyfrom about 0.3 hr⁻¹ to about 5 hr⁻¹; and a molar ratio of treatedbenzene to propylene in the alkylation reactor of from about 0.1:1 toabout 30:1, more preferably from about 1:1 to about 20:1 molar.

In the reaction mechanism of the present invention, the alkylationreactor effluent may contain excess aromatic feed, monoalkylatedproduct, polyalkylated products, and various impurities. The aromaticfeed is recovered by distillation and recycled to the alkylationreactor. Usually a small bleed is taken from the recycle stream toeliminate unreactive impurities from the loop. The bottoms from thedistillation may be further distilled to separate monoalkylated productfrom polyalkylated products and other heavies.

The polyalkylated products separated from the alkylation reactoreffluent may be reacted with additional aromatic feed in atransalkylation reactor, separate from the alkylation reactor, over asuitable transalkylation catalyst. The transalkylation catalyst maycomprise one or a mixture of crystalline molecular sieves having thestructure of zeolite Beta, zeolite Y, mordenite or an MWW frameworkstructure type material, described above.

Relative Activity

The catalytic composition for use in the present invention may have aRelative Activity measured as an RA₂₂₀ of at least 8.6, for example from8.6 to 12.0, or RA₁₈₀ of at least 3.5, for example from 3.5 to 6.0,allowing operation at lower reaction pressures, e.g. a reactor outletpressure of about 3102 kPa or less, and lower alkylating agent, e.g.ethylene or propylene, feed supply pressure of 3102 kPa or less, e.g.2758 kPa or less. As used herein, the Relative Activity measured asRA₂₂₀ or RA₁₈₀ is determined by a method similar to that described by S.Folger in Elements of Chemical Reactor Engineering, 2^(nd) Edition,pages 406-407. In this method using an adiabatic reactor, an energybalance is used to relate the temperature rise to the conversion ofethylene. With thermocouple positions, inlet temperature, pressure andconversions known, the Relative Activity of the catalyst may bedetermined using a differential reactor analysis. For this analysis, theRelative Activity is calculated by the percent temperature rise dividedby the percentage of the bed length. In short, Relative Activity(RA)=ΔT/L, wherein ΔT is percent temperature rise and L is percentage ofthe bed length. When inlet temperature to the adiabatic reactor is 180°C., the value of RA is RA₁₈₀ and when inlet temperature to the adiabaticreactor is 220° C., the value of RA is RA₂₂₀.

This RA determination is exemplified by the following experiments inwhich an adiabatic ¾″ pipe reactor with multipoint thermocouples isloaded with approximately 28 grams of a specified catalyst. The catalystis tightly packed between inert alumina beds to provide good flowdistribution. A feed comprising ethylene and benzene (1:1.5 molar),heated to an inlet temperature of 180 or 220° C., passes through the bedof catalyst enabling reaction and exits the reactor as effluent. A partof the effluent is recycled back to the feed in order to maintain anadiabatic temperature rise of approximately 40° C. The recycle to feed(weight) ratio is maintained at 6 to 1 to maintain liquid phaseconditions. The multipoint thermocouple in the bed consists of sixthermocouples that are used to measure the temperature at 6 pointsinside the bed. Results are described in the following table withCatalyst A and B being the same MWW structure material.

Thermocouple Inlet Position Percent Temperature (Percentage ofTemperature Catalyst (° C.) Bed) Rise RA B (Lower Activity) 180 4.9%9.0%  1.8 B (Lower Activity) 220 4.9% 32% 6.5 A (Higher Activity) 1804.4% 23% 5.2 A (Higher Activity) 220 4.4% 47% 10.7

EXAMPLES

Non-limiting examples of the invention involving an improved alkylationmechanism are described with reference to the following experiments. Inthese experiments, two separate beds, a treatment zone and an alkylationreaction zone are placed in series. The first bed (treatment zone)containing a particular treatment composition is used for treatment ofbenzene containing nitrogen compounds (catalyst poisons) to protect adownstream alkylation reaction zone capable of doing alkylation reactionchemistry. The benzene is fed to the treatment zone along with ethylene.The effluent of the treatment zone is then mixed with ethylene and fedto the alkylation reaction zone containing alkylation catalyst. Thenumber of days of stable alkylation operation (run length) is determinedfrom when deactivation is first observed to occur in the alkylationreaction zone. Deactivation of catalyst in the alkylation reaction zonethus correlates to the run length of the treatment composition and itsapparent capacity (at constant flow conditions). Once the treatmentcomposition no longer retains poisons (slippage), it needs to either beregenerated or replaced. Examples 1-4 below demonstrate the efficacy oftreatment compositions comprising the surface area/surface volume ratiorequired of the materials to be used herein. The poison capacities ofthe treatment compositions in the treatment zones are calculated fromthe time on stream and the time at which catalyst deactivation isobserved in the alkylation reaction zone.

The surface area/surface volume ratio was determined by using an opticalprocess to measure particle dimensions and particle curvature using theAdvanced Laboratory Imaging and Analysis System (ALIAS) obtained fromCascade Data Systems of Wilsonville, Oreg.

Example 1

A 16 gram quantity of material formulated as 1/20 inch (0.13 cm)quadrulobe particles comprising MCM-49 (which has MWW frameworkstructure) was placed in both the treatment zone (as a treatmentcomposition) and the alkylation reaction zone (as a catalyticcomposition). The quadrulobe material had a surface area/surface volumeratio of approximately 180-220 in⁻¹ (71-87 cm⁻¹). Benzene comprising 0.3wppm of Nitrogen (hereinafter referred to as “N”) in the form ofN-formylmorphaline and ethylene were fed to the treatment zone atambient pressure, a benzene/ethylene molar ratio between 50:1 and 70:1,approximately 60:1, a WHSV of approximately 21 hr⁻¹ on a benzene basisand 180° C. (liquid phase). The effluent from the treatment zone, mixedwith ethylene, was then fed to the alkylation reaction zone maintainedat a temperature of 180° C., with the mixture in the liquid phase,benzene/ethylene molar ratio of 18:1, and with a WHSV of 0.77 hr⁻¹ basedon ethylene. The catalytic composition in the reaction zone did notdeactivate for 5 to 7 days. Therefore, the poison capacity of thetreatment composition in the treatment zone was calculated to beapproximately 900-1000 wppm of N.

Example 2

A 16 gram quantity of material formulated as 1/20 inch (0.13 cm)quadrulobe particles comprising MCM-49 (which has MWW frameworkstructure), crushed to 200-250 micron-sized particles, was placed in thetreatment zone (as a treatment composition), and a 28 gram quantity ofmaterial formulated as 1/20 inch (0.13 cm) quadrulobe particlescomprising MCM-49 was placed in the alkylation reaction zone (as acatalytic composition). The crushed material in the treatment zone(treatment composition) had a surface area/surface volume ratio ofapproximately 600-770 in⁻¹ (236-303 cm⁻¹). The quadrulobe material inthe alkylation reaction zone (catalytic composition) had a surfacearea/surface volume ratio of approximately 180-220 in⁻¹ (71-87 cm⁻¹).Benzene comprising 0.3 wppm of N in the form of N-formylmorphaline andethylene were fed to the treatment zone at ambient pressure, abenzene/ethylene molar ratio between 9:1 and 26:1, a WHSV ofapproximately 20 hr⁻¹ based on benzene and 180° C. (liquid phase). Theeffluent from the treatment zone, mixed with ethylene, was then fed tothe reaction zone maintained at a temperature of 220° C. with themixture in the liquid phase, the benzene/ethylene molar ratio ofapproximately 20:1, and with a WHSV of approximately 0.85 hr⁻¹ based onethylene. The catalytic composition in the reaction zone did notdeactivate for 8 to 9 days. Therefore, the poison capacity of thetreatment composition in the treatment zone was calculated to beapproximately 1200 wppm of nitrogen (N).

Example 3

A 16 gram quantity of treatment composition comprising zeolite Beta(which has *BEA framework structure) formulated as 1/20 inch (0.13 cm)quadrulobe particles with a surface area/surface volume ratio of 180-220in⁻¹ (71-87 cm⁻¹) was placed in the treatment zone, and a 28 gramquantity of material formulated as 1/20 inch (0.13 cm) quadrulobeparticles comprising MCM-49 was placed in the alkylation reaction zone.Benzene comprising 0.3 wppm of N in the form of N-formylmorphaline andethylene was fed to the treatment zone at ambient pressure, abenzene/ethylene molar ratio of approximately 55:1, a WHSV of 21 hr⁻¹based on benzene and 180° C. (liquid phase). (However the selectivity ofthe treatment composition was very poor, producing approximately 2.5 to4.0 times the amount of diethylbenzene as an MWW catalyst.) The effluentfrom the treatment zone, mixed with ethylene, was then fed to thereaction zone maintained at a temperature of 180° C., with the mixturein the liquid phase, a benzene/ethylene molar ratio of 18:1, and with aWHSV of approximately 0.77 hr⁻¹ based on benzene. The catalyticcomposition in the reaction zone did not deactivate for 38-42 days.Therefore, the poison capacity of the treatment composition in thetreatment zone was calculated to be approximately 5950 wppm of N.

Example 4

A 16 gram quantity of treatment composition comprising faujasite (whichhas FAU framework structure) formulated as 1/16 inch (0.16 cm) cylinderparticles with a surface area/surface volume ratio of a surfacearea/surface volume ratio of 70-100 in⁻¹ (28-39 cm⁻¹) was placed in thetreatment zone (as a treatment composition), and a 28 gram quantity ofmaterial formulated as 1/20 inch (0.13 cm) quadrulobe particlescomprising an MWW catalyst was placed in the alkylation reaction zone(as a catalytic composition). Benzene comprising 0.3 wppm of N in theform of N-formylmorphaline and ethylene were fed to the treatment zoneat ambient pressure, a benzene/ethylene molar ratio of approximately75:1, a WHSV of 21 hr⁻¹ based on benzene and 170° C. (liquid phase).(However, the selectivity of the treatment composition was very poor,producing approximately 5.0 times the amount of diethylbenzenes as anMWW catalyst). The effluent from the treatment zone, mixed withethylene, was then fed to the reaction zone maintained at a temperatureof 220° C., with the mixture in the liquid phase, benzene/ethylene molarratio of 18:1, and with a WHSV of approximately 0.85 hr⁻¹ based onbenzene. The catalytic composition in the reaction zone did notdeactivate for 13-15 days. Therefore, the poison capacity of thetreatment composition in the treatment zone was calculated to beapproximately 2000 wppm of N.

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this invention and for all jurisdictions in which suchincorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and may be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

1. A process for producing an alkylated aromatic compound stream from atleast one partially untreated alkylatable aromatic compound streamhaving catalyst poisons comprising a compound having nitrogen as anelement, the process comprising the steps of: (a) feeding said untreatedalkylatable aromatic compound stream having said catalyst poisons and aportion of an alkylating agent stream in the liquid phase to a treatmentzone having a treatment composition comprising a zeolite having a FAU ora MOR framework type; (b) contacting said untreated alkylatable aromaticcompound stream and said alkylating agent stream with said treatmentcomposition in said treatment zone separate from an alkylation reactionzone under liquid phase treatment conditions to remove at least aportion of said catalyst poisons and to alkylate at least a portion ofsaid alkylatable aromatic compound to form a treated effluent streamwhich comprises treated alkylatable aromatic compound, an alkylatedaromatic compound and a reduced amount of catalyst poisons, wherein saidtreatment composition has a surface area/surface volume ratio in therange of 180 in (71 cm⁻¹) to 220 in⁻¹ (87 cm⁻¹), said liquid phasetreatment conditions include a temperature of from about 30° C. to about300° C. and a pressure from about 101 kPa to about 4601 kPa, and a molarratio of untreated alkylatable aromatic compound to alkylating agent ofgreater than or equal to about 50:1; and (c) contacting said treatedalkylatable aromatic compound in said effluent stream and an additionalportion of said alkylating agent stream with a catalyst composition insaid alkylation reaction zone separate from said treatment zone under atleast partial liquid phase catalytic conversion conditions to form analkylated effluent stream which comprises additional alkylated aromaticcompound, wherein said catalyst composition comprises a porouscrystalline material having a framework structure type selected from thegroup consisting of FAU, *BEA, MOR, MWW and mixtures thereof, whereinsaid at least partial liquid phase catalytic conversion conditionsinclude a temperature of from about 100° C. to about 300° C., a pressurefrom about 689 kPa to about 4601 kPa, a molar ratio of treatedalkylatable aromatic compound to alkylating agent of from about 0.01:1to about 25:1, and a feed weight hourly space velocity (WHSV) based onalkylating agent of from about 0.5 to about 500 hr⁻¹.
 2. The process ofclaim 1, wherein said porous crystalline material having said FAUframework structure type is faujasite, zeolite Y, Ultrastable Y (USY),Dealuminized Y (Deal Y), Rare Earth Y (REY), Ultrahydrophobic Y (UHP-Y)or a mixture thereof.
 3. The process of claim 1, wherein said porouscrystalline material having said *BEA framework structure type iszeolite beta.
 4. The process of claim 1, wherein said porous crystallinematerial having said MOR framework structure type is mordenite,TEA-mordenite or a mixture thereof.
 5. The process of claim 1, whereinsaid porous crystalline material having said MWW framework structuretype has an X-ray diffraction pattern including d-spacing maxima at12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms in as-synthesizedor calcined form.
 6. The process of claim 1, wherein said porouscrystalline material having MWW framework structure type is PSH-3,SSZ-25, ERB-1, ITQ-1, ITQ-2, ITQ-30, MCM-22, MCM-36, MCM-49, MCM-56,UZM-8, EMM-10, EMM-12, EMM-13 or mixtures thereof.
 7. The process ofclaim 1, wherein said alkylatable aromatic compound is selected from thegroup consisting of benzene, naphthalene, anthracene, naphthacene,perylene, coronene, phenanthrene and mixtures thereof.
 8. The process ofclaim 1, wherein said alkylatable aromatic compound is benzene, saidalkylating agent is ethylene and said alkylated aromatic compound isethylbenzene.
 9. The process of claim 1, wherein said alkylatablearomatic compound is benzene, said alkylating agent is propylene andsaid alkylated aromatic compound is cumene.
 10. The process of claim 1,wherein said alkylatable aromatic compound is benzene, said alkylatingagent is butene and said alkylated aromatic compound issec-butylbenzene.
 11. The process of claim 1, wherein said alkylatablearomatic compound is benzene, said alkylating agent is ethylene, saidalkylated aromatic compound is ethylbenzene, and said at least partialliquid phase conversion conditions include a temperature of from about100° C. to about 280° C., a pressure of about 3102 kPa or less, a weighthourly space velocity (WHSV) based on the ethylene of from about 0.1 toabout 20 hr⁻¹, and a ratio of benzene to ethylene in the alkylationreactor of from about 0.5:1 to about 20:1 molar.
 12. The process ofclaim 11, wherein said porous crystalline material having said MWWframework structure type has an X-ray diffraction pattern includingd-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07Angstroms.
 13. The process of claim 11, wherein said porous crystallinematerial having MWW framework structure type is PSH-3, SSZ-25, ERB-1,ITQ-1, ITQ-2, ITQ-30, MCM-22, MCM-36, MCM-49, MCM-56, UZM-8, EMM-10,EMM-12, EMM-13 or mixtures thereof.
 14. The process of claim 1, whereinsaid alkylatable aromatic compound comprises benzene, said alkylatingagent is propylene, said alkylated aromatic compound comprises cumene,and said at least partial liquid phase conversion conditions include atemperature of less than about 200° C., a pressure of about 3102 kPa orless, a weight hourly space velocity (WHSV) based on propylenealkylating agent of from about 0.1 hr⁻¹ to about 250 hr⁻¹, and a ratioof benzene to propylene in the alkylation reactor of from about 0.5:1 toabout 20:1 molar.
 15. The process of claim 14, wherein said porouscrystalline material having said MWW framework structure type has anX-ray diffraction pattern including d-spacing maxima at 12.4±0.25,6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms.
 16. The process of claim14, wherein said porous crystalline material having MWW frameworkstructure type is PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, ITQ-30, MCM-22,MCM-36, MCM-49, MCM-56, UZM-8, EMM-10, EMM-12, EMM-13 or mixturesthereof.
 17. The process of claim 1, wherein said treatment conditionsof contacting step (a) includes a treatment weight hourly space velocity(WHSV) based on the untreated alkylatable aromatic compound in the rangefrom about 5 to 70 hr-1.
 18. The process of claim 1, said treatmentcomposition absorbs greater than 900 wppm N-formyl morpholine (NFM)based on the weight of the treatment composition.